Mossbauer resonance absorption

The Mossbauer effect, discovered by Rudolf L. Mossbauer in 1957, can in short be described as the recoil-free emission and resonant absorption of gamma radiation by nuclei. In the case of iron, the source consists of Co, which decays with a half-life of 270 days to an excited state of Fe (natural abundance in iron 2%). The latter, in turn, decays rapidly to the first excited state of this isotope. The final decay generates a 14.4 keV photon and a very narrow natural linewidth of the order of nano eV. 

Fig. 2.1 Nuclear resonance absorption of y-rays (Mossbauer effect) for nuclei with Z protons and N neutrons. The top left part shows the population of the excited state of the emitter by the radioactive decay of a mother isotope (Z, N ) via a- or P-emission, or K-capture (depending on the isotope). The right part shows the de-excitation of the absorber by re-emission of a y-photon or by radiationless emission of a conversion electron (thin arrows labeled y and e , respectively)...

Resonant y-ray absorption is directly connected with nuclear resonance fluorescence. This is the re-emission of a (second) y-ray from the excited state of the absorber nucleus after resonance absorption. The transition back to the ground state occurs with the same mean lifetime t by the emission of a y-ray in an arbitrary direction, or by energy transfer from the nucleus to the K-shell via internal conversion and the ejection of conversion electrons (see footnote 1). Nuclear resonance fluorescence was the basis for the experiments that finally led to R. L. Mossbauer s discovery of nuclear y-resonance in ir ([1-3] in Chap. 1) and is the basis of Mossbauer experiments with synchrotron radiation which can be used instead of y-radiation from classical sources (see Chap. 9). 

Fig. 2.6 Schematic illustration of a Mossbauer transmission experiment in five steps. The Absorption bars indicate the strength of recoilless nuclear resonant absorption as determined by the overlap of emission and absorption lines when the emission line is shifted by Doppler modulation (velocities Uj,. .., 1)5). The transmission spectrum T v) is usually normalized to the transmission T oo) observed for v oo by dividing T(v)IT(oo). Experimental details are found in Chap. 3...

For nuclear y-resonance absorption to occur, the y-radiation must be emitted by source nuclei of the same isotope as those to be explored in the absorber. This is usually a stable isotope. To obtain such nuclei in the desired excited meta-stable state for y-emission in the source, a long-living radioactive parent isotope is used, the decay of which passes through the Mossbauer level. Figure 3.6a shows such a transition cascade for Co, the y-source for Fe spectroscopy. The isotope has a half-life time //2 of 270 days and decays by K-capmre, yielding Fe in the 136 keV excited state ( Co nuclei capmre an electron from the K-shell which reduces the... 

Scattered radiation. In a transmission experiment, the Mossbauer sample emits a substantial amount of scattered radiation, originating from XRF and Compton scattering, but also y-radiation emitted by the Mossbauer nuclei upon de-excitation of the excited state after resonant absorption. Since scattering occurs in 4ti solid angle, the y-detector should not be positioned too close to the absorber so as not to collect too much of this unwanted scattered radiation. The corresponding pulses may not only uimecessarily overload the detector and increase the counting dead time, but they may also affect the y-discrimination in the SCA and increase the nonresonant background noise. 

The isomer shift of a resonance line (or the centroid of a line multiplet) in an experimental Mossbauer spectrum in terms of the Doppler velocity (mm s ) necessary to achieve resonance absorption is given by... 

Nuclear resonance absorption for the 136 keV transition has been established by Steiner et al. [174]. The authors used a metal source and an absorber of metallic tantalum to determine the mean lifetime of the 136 keV level from the experimental line width ( 52.5 mm s for zero effective absorber thickness) and found a value of 55 ps. This has been the only report so far on the use of the 136 keV excited state of Ta for Mossbauer experiments. 

There are two iridium isotopes, ir and Ir, suitable for Mossbauer spectroscopy. Each of them possesses two nuclear transitions with which nuclear resonance absorption has been observed. Figure 7.58 (from [266]) shows the (simplified) nuclear decay schemes for both iridium Mossbauer isotopes the Mossbauer transitions are marked therein with bold arrows. The relevant nuclear data known to date for the four Mossbauer transitions are collected in Table 7.1 at the end of the book. 

It is a matter of historical interest that Mossbauer spectroscopy has its deepest root in the 129.4 keV transition line of lr, for which R.L. Mossbauer established recoilless nuclear resonance absorption for the first time while he was working on his thesis under Prof. Maier-Leibnitz at Heidelberg [267]. But this nuclear transition is, by far, not the easiest one among the four iridium Mossbauer transitions to use for solid-state applications the 129 keV excited state is rather short-lived (fi/2 = 90 ps) and consequently the line width is very broad. The 73 keV transition line of lr with the lowest transition energy and the narrowest natural line width (0.60 mm s ) fulfills best the practical requirements and therefore is, of all four iridium transitions, most often (in about 90% of all reports published on Ir Mossbauer spectroscopy) used in studying electronic stractures, bond properties, and magnetism. 

It is much more difficult to observe the Mossbauer effect with the 130 keV transition than with the 99 keV transition because of the relatively high transition energy and the low transition probability of 130 keV transition, and thus the small cross section for resonance absorption. Therefore, most of the Mossbauer work with Pt, published so far, has been performed using the 99 keV transition. Unfortunately, its line width is about five times larger than that of the 130 keV transition, and hyperfine interactions in most cases are poorly resolved. However, isomer shifts in the order of one-tenth of the line width and magnetic dipole interaction, which manifests itself only in line broadening, may be extracted reliably from Pt (99 keV) spectra. 

The first Mossbauer measurements involving mercury isotopes were reported by Carlson and Temperley [481], in 1969. They observed the resonance absorption of the 32.2 keV y-transition in (Fig. 7.87). The experiment was performed with zero velocity by comparing the detector counts at 70 K with those registered at 300 K. The short half-life of the excited state (0.2 ns) leads to a natural line width of 43 mm s Furthermore, the internal conversion coefficient is very large (cc = 39) and the oi pj precursor populates the 32 keV Mossbauer level very inefficiently ( 10%). 

Mossbauer spectroscopy can be used for in situ study of electrodes containing nuclei capable of resonance absorption of y radiation for practical systems, primarily the 57Fe isotope is used (passivation layers on iron electrodes, adsorbed iron complexes, etc.). It yields valuable information on the electron density on the iron atom, on the composition and symmetry of the coordination sphere around the iron atom and on its oxidation state. 

The recoilless nuclear resonance absorption of y-radiation (Mossbauer effect) has been verified for more than 40 elements, but only some 15 of them are suitable for practical applications [33, 34]. The limiting factors are the lifetime and the energy of the nuclear excited state involved in the Mossbauer transition. The lifetime determines the spectral line width, which should not exceed the hyperfine interaction energies to be observed. The transition energy of the y-quanta determines the recoil energy and thus the resonance effect [34]. 57Fe is by far the most suited and thus the most widely studied Mossbauer-active nuclide, and 57Fe Mossbauer spectroscopy has become a standard technique for the characterisation of SCO compounds of iron. 

Mossbauer spectroscopy The Mossbauer effect is resonance absorption of 7 radiation of a precisely defined energy, by specific nuclei. It is the basis of a form of spectroscopy used for studying coordinated metal ions. The principal application in bioinorganic chemistry is Fe. The source for the 7 rays is Co, and the frequency is shifted by the Doppler effect, moving it at defined velocities (in mm/s) relative to the sample. The parameters derived from the Mossbauer spectrum (isomer shift, quadrupole splitting, and the hyperfine coupling) provide information about the oxidation, spin and coordination state of the iron. 

Mossbauer spectroscopy, also called recoil-free nuclear resonance absorption, depends upon resonant absorption of y-rays emitted by a radioactive source by atomic nuclei.120 The phenomenon was initially difficult to observe, but the German physicist Mossbauer devised a way in which to record the absorption of a quantum of energy equal to the difference in two energy states of the atomic nucleus. The method depends upon a Doppler effect observed when the sample or source moves. Consequently, Mossbauer spectra, such as that in Fig. 16-18, are plots of absorp-... 

Resonant absorption of the modulated y ray takes place by an atom of the same Mossbauer isotope located in an absorber. 

B. MOssbauer Spectroscopy Resonant Absorption and Perturbations of Nuclear Levels... 

Most often the transmission mode is found to be the most convenient in Mossbauer spectroscopy, i.e., the y radiation passes from the source through the absorber, and the attenuation of the primary beam is measured at the various Doppler velocities. However, there are a number of cases where a "scattering geometry may be advantageous (SO). The basis for this geometry lies in those processes that take place after resonant absorption of y radiation by the Mossbauer isotope. Specifically, after excitation the Mossbauer isotope may reemit the y ray, or it may decay by emission of internal conversion electrons and X rays [with the probability of internal conversion equal to a/(l + a)]. 

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